US7261779B2 - System, method, and apparatus for continuous synthesis of single-walled carbon nanotubes - Google Patents
System, method, and apparatus for continuous synthesis of single-walled carbon nanotubes Download PDFInfo
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- US7261779B2 US7261779B2 US10/455,767 US45576703A US7261779B2 US 7261779 B2 US7261779 B2 US 7261779B2 US 45576703 A US45576703 A US 45576703A US 7261779 B2 US7261779 B2 US 7261779B2
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- C01B32/15—Nano-sized carbon materials
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- C01B32/16—Preparation
- C01B32/162—Preparation characterised by catalysts
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- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
- C01B32/164—Preparation involving continuous processes
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- D—TEXTILES; PAPER
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- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
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- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J2219/0803—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
- B01J2219/0805—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges
- B01J2219/0807—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges involving electrodes
- B01J2219/0809—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges involving electrodes employing two or more electrodes
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J2219/0803—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
- B01J2219/0805—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges
- B01J2219/0807—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges involving electrodes
- B01J2219/0837—Details relating to the material of the electrodes
- B01J2219/0839—Carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J2219/0873—Materials to be treated
- B01J2219/0879—Solid
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J2219/0894—Processes carried out in the presence of a plasma
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J2219/0894—Processes carried out in the presence of a plasma
- B01J2219/0898—Hot plasma
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/02—Single-walled nanotubes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/70—Nanostructure
- Y10S977/734—Fullerenes, i.e. graphene-based structures, such as nanohorns, nanococoons, nanoscrolls or fullerene-like structures, e.g. WS2 or MoS2 chalcogenide nanotubes, planar C3N4, etc.
- Y10S977/742—Carbon nanotubes, CNTs
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/70—Nanostructure
- Y10S977/734—Fullerenes, i.e. graphene-based structures, such as nanohorns, nanococoons, nanoscrolls or fullerene-like structures, e.g. WS2 or MoS2 chalcogenide nanotubes, planar C3N4, etc.
- Y10S977/742—Carbon nanotubes, CNTs
- Y10S977/75—Single-walled
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/70—Nanostructure
- Y10S977/773—Nanoparticle, i.e. structure having three dimensions of 100 nm or less
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/70—Nanostructure
- Y10S977/773—Nanoparticle, i.e. structure having three dimensions of 100 nm or less
- Y10S977/775—Nanosized powder or flake, e.g. nanosized catalyst
- Y10S977/777—Metallic powder or flake
Definitions
- the present invention relates in general to an improved process for manufacturing carbon nanotubes and, in particular, to an improved system, method, and apparatus for continuous synthesis of single-walled carbon nanotubes.
- swcnt single-walled carbon nanotubes
- CVD chemical vapor deposition
- Some of these prior art processes have also combined plasma generation, thermal annealing, and the use of various transition metal catalyst supports with one of the three techniques. See, e.g., U.S. Pat. No. 6,451,175 to Lal; U.S. Pat. No. 6,422,450 to Zhou; U.S. Pat. No. 6,232,706 to Dai; and U.S. Pat. No. 6,221,330 to Moy.
- the present invention comprises a system, method, and apparatus for producing carbon allotropes such as single-walled carbon nanotubes (swcnt) in a continuous manner.
- One embodiment of the invention uses a three-step process of carbon plasma generation, plasma stabilization, and product spray deposition, all of which are scalable to large, industrial volume production levels.
- the plasma may be generated in several continuous manners, including electrical resistance heating and/or electron beam vaporization of feedstock, and catalytic pyrolysis of organic precursors.
- the plasma is stabilized, for example, with radio frequency energy from inductance coils.
- a transition metal catalyst and associated required catalyst support are used to form the end product of swcnt.
- One advantage and application of the present invention is the continuous, large scale production of single wall carbon nanotubes for manufacturing high performance structures.
- This method is superior to prior art processes because it provides for (i.) the continuous generation of carbon plasma, (ii.) stabilization of the carbon plasma for homogenization of the reactant mixture and transport of a high concentration of carbon plasma to the product formation zone, and (iii.) a continuous operation, flow-through reactor design.
- the entire apparatus is designed so that it can be mounted vertically, such that continuous deposition of product can be precisely applied to a structure using an overhead robotic arm.
- the initiation of the carbon plasma may be accomplished by several methods.
- One option is vaporization of a resistively-heated graphite element to create a thermal plasma.
- Carbon or graphite feedstock which are readily available from commercial suppliers as rod stock, fiber, or in a special-designed geometry, is continuously fed over two oppositely-charged electrodes. Low voltage, high current, electric power is then passed through the feedstock. This results in rapid resistance-heating of the feedstock.
- the electric power is regulated by feedback control from an ultra-high temperature pyrometer, which measures the element temperature in order to maintain a peak temperature of around 3000° C.
- the reactor is closed and sealed with a reduced pressure inert atmosphere of continuously-flowing inert gas.
- Another method for generating the carbon plasma is to vaporize the feedstock with an electron beam.
- This method uses an e-beam focused on, for example, a graphite feedstock to generate a carbon plasma. This design allows localized directional control of the energy and efficient energy transfer because of the highly conductive nature of the graphite.
- Another method for generating the carbon plasma is catalytic pyrolysis of organic precursors. This is accomplished using a continuous feed of hydrocarbons in an inert gas stream through a heated zone or by passing through a plasma jet.
- the heated zone can be accomplished using a device like a tube furnace or a tungsten coil.
- the plasma jet can be accomplished using a cathode/anode plasma gun using a high voltage discharge to dissociate and ionize the hydrocarbon feedstock.
- the second step in the process of the present invention is plasma stabilization.
- Classical chemical engineering reactor design specifies that reactants should form a homogeneous mixture for optimization of product yield, purity, and reaction rate.
- the stabilization step has been completely ignored in the processes reported in the open literature to date.
- This stabilization step homogenizes the plasma energy density and concentration, leading to a more efficient reactor.
- the stabilization of the carbon plasma is achieved using inductively coupled radio frequency (rf) energy or microwave (mw) energy from a wave guide.
- the power and frequency are controlled such that the carbon plasma remains stable in the vapor phase.
- Electrical resistance heaters also can be added inside the reactor to maintain a chamber temperature of up to 1700° C. This additional thermal energy may be used to reduce the required rf or mw energy needed to stabilize the carbon plasma, and to also promote a higher concentration of carbon vapor in the reactor. Stabilization of the plasma occurs immediately downstream from the generated plasma.
- the third and last stage of the reactor is the swcnt formation zone.
- One of the important elements of the formation zone is a transition metal catalyst and associated catalyst support.
- the formation zone may have variations of geometry and supporting equipment that will affect the rate and purity of the swcnt production.
- the formation zone is immediately downstream from the plasma stabilization zone.
- One of the simplest designs for the swcnt formation zone is to transport the stabilized plasma through a catalyst screen in the deposition nozzle.
- the catalyst screen can be made from a variety of materials, depending upon the operating temperature of the stabilization zone.
- Some of these materials include ceramic fiber mesh with a transition metallic catalyst coating, a metallic screen made directly from the transition metallic catalyst, a carbon fiber coated with a transition metallic catalyst, and/or a porous silica membrane with a transition metallic catalyst deposited on the “exit” side of the membrane.
- the flow rate, carbon concentration, pressure, and temperature should be carefully regulated. Differential pressure is used to push the swcnt product out the exit port.
- Another method is to introduce the transition metal catalyst into the formation zone as a gas phase organometallic compound or as metal nanoparticles. In this manner, the formation of swcnt occurs in the flowing reactant stream and can be ejected for deposition on a surface. Yet another method is to coat a substrate with a transition metal catalyst and allow the formation zone to occur just on the outside of the reactor on the substrate.
- FIGS. 1 a and 1 b are sectional diagrams of one embodiment of a system, method, and apparatus for continuous synthesis of single-walled carbon nanotubes, and is constructed in accordance with the present invention.
- FIG. 2 is an isometric diagram of another embodiment of a system, method, and apparatus for continuous synthesis of single-walled carbon nanotubes, and is constructed in accordance with the present invention.
- FIG. 3 is schematic isometric view of the system, method, and apparatus of FIG. 2 mounted to a robotic arm for one application, and is constructed in accordance with the present invention.
- FIG. 4 is an isometric view of the system, method, and apparatus of FIG. 2 , and is constructed in accordance with the present invention.
- FIG. 5 is schematic isometric view of the system, method, and apparatus of FIG. 2 mounted to a robotic arm for use in a manufacturing operation, and is constructed in accordance with the present invention.
- FIG. 6 is a schematic diagram of an alternate embodiment of a system and process for continuous synthesis of single-walled carbon nanotubes constructed in accordance with the present invention.
- FIG. 7 is a schematic diagram of another alternate embodiment of a system and process for continuous synthesis of single-walled carbon nanotubes constructed in accordance with the present invention.
- FIG. 8 is a schematic diagram of another alternate embodiment of a system and process for continuous synthesis of single-walled carbon nanotubes constructed in accordance with the present invention.
- FIGS. 1-8 a system, method, and apparatus for producing single-walled carbon nanotubes (swcnt) in a continuous manner is shown.
- some of the embodiments of the present invention use a three-step process of carbon plasma generation, plasma stabilization, and product deposition, all of which are scalable to large, industrial volume production levels.
- FIGS. 1 a and 1 b depict one embodiment of an apparatus 11 for producing single-walled carbon nanotubes.
- Apparatus 11 comprises a continuous operation, flow-through reactor 13 having an initial region 15 ( FIG. 1 b ), a plasma stabilization region 17 , and a product formation region 19 .
- the product formation region 19 is located immediately downstream from the plasma stabilization region 17 .
- a feedstock 21 is located in the initial region 15 and is designed and adapted to be continuously supplied to the reactor 13 .
- the feedstock 21 may comprise many different types and forms of material, but is preferably a carbon or graphite fiber feedstock, graphite electrodes, and may be supplied in the form of rod stock or fiber, for example.
- Each of the embodiments of the present invention includes means for generating a continuous stream of carbon plasma 22 from the feedstock 21 .
- apparatus 11 utilizes an electrical resistance heater 23 to form the plasma 22 .
- the electrical resistance heater 23 is mounted to the reactor 13 for passing low voltage, high current, electric power through the feedstock 21 over two oppositely-charged electrodes 24 , 25 , such that the feedstock 21 is rapidly resistance-heated.
- the electric power is regulated by feedback control 27 from an ultra-high temperature pyrometer 29 for measuring a temperature of the feedstock 21 to maintain a peak temperature of approximately 3000° C.
- the apparatus 111 has means for generating the plasma 122 that comprises an electron beam device 123 that vaporizes the feedstock 121 .
- An electron beam is focused on a graphite target with sufficient energy and spot size to rapidly heat the graphite target, creating a thermal carbon plasma. Beam dithering and graphite feed rate is optimized to provide complete consumption of the feedstock.
- apparatus 111 comprises a continuous operation, flow-through reactor 113 having an initial plasma generation region 113 , a plasma stabilization region 115 , and a product formation region 117 .
- a feedstock 121 is continuously supplied to the plasma generation zone 113 for generating a continuous stream of carbon plasma 122 from the feedstock 121 .
- the apparatus 111 further comprises a reduced pressure inert atmosphere of continuously-flowing gas through supply 133 .
- Apparatus 111 also includes inductance coils 141 for stabilizing the carbon plasma in a vapor phase with radio frequency energy.
- apparatus 111 further comprises optional electrical resistance heaters for applying thermal energy to reduce the radio frequency energy required to stabilize the carbon plasma, and to promote a higher concentration of carbon vapor in the reactor.
- apparatus 111 includes a transition metal catalyst and an associated catalyst support 169 for forming a product 165 .
- the transition metal catalyst and the associated catalyst support comprise a catalyst screen 169 in a deposition nozzle 171 .
- the reactor 13 further comprises a reduced pressure inert atmosphere 31 of continuously-flowing gas through supply 33 .
- the gas may comprise argon, helium, nitrogen, or other inert gases.
- Control of a feed rate of the feedstock 21 , the pressure of the argon gas 31 , and the electric power level results in control of partial vaporization of the feedstock 21 to a level such that enough carbon remains to facilitate a continuous line feed, as shown.
- As physical contact is required between the two electrodes 24 , 25 and some of the carbon feedstock is vaporized it is important to not vaporize all of the feedstock, thereby leaving sufficient material to provide continuous contact of the feedstock with the trailing and forward electrodes.
- Apparatus 11 also includes inductance coils 41 mounted to the reactor 13 for stabilizing the carbon plasma 22 in a vapor phase in the plasma stabilization region 17 with radio frequency energy via controller 43 .
- the carbon plasma is stabilized by controlling the power and a frequency of the radio frequency energy, such that the carbon plasma is stabilized for homogenization of a reactant mixture and transport of a high concentration of the carbon plasma to the product formation region 19 .
- the apparatus 11 further comprises electrical resistance heaters 51 mounted to the reactor 13 for applying thermal energy inside the reactor 13 to maintain a reactor temperature of up to approximately 1700° C. In this way, the thermal energy reduces the radio frequency energy required to stabilize the carbon plasma 22 , and promotes a higher concentration of carbon vapor in the reactor 13 .
- a transition metal catalyst 61 (see catalyst feed 61 a in FIG. 6 ) on an associated catalyst support 69 for forming a product 65 are used to spray deposit material.
- swcnt are grown on the catalyst particles they are entrained downstream towards the exit port of the reactor. Individual swcnt filaments physically bond to each other through van der Waals attraction and form bundles of filaments. As the bundles increase in size, their mass increases and they are pulled from the catalyst support 69 from the force of the entrainment of the flow stream. The flow stream is directed towards a build surface 71 where the swcnt bundles are deposited. The flow rate, carbon concentration, pressure, flow rate, and temperature are carefully regulated.
- the transition metal catalyst and the associated catalyst support comprise a catalyst screen 69 (see catalyst and support screen 69 b in FIG. 7 ) in a deposition nozzle.
- the catalyst screen 69 is formed from a material that is selected based upon an operating temperature of the plasma stabilization region 17 .
- the material used to form the catalyst screen 69 is selected from among, for example, ceramic fiber mesh with a transition metallic catalyst coating, a metallic screen made directly from the transition metal catalyst (see catalyst and support screen 69 b in FIG. 7 ), a carbon fiber coated with the transition metallic catalyst, or a porous silica membrane with the transition metallic catalyst deposited on an exit side of the membrane.
- the present invention such as apparatus 111
- a system 301 which comprises a robotic arm 303 for supporting and manipulating the apparatus 111 such that continuous deposition of the product is applied to a workpiece 305 during manufacturing and assembly thereof.
- the apparatus 111 , robotic arm 303 , and workpiece 305 are located inside a pressure and atmosphere controlled chamber 307 .
- apparatus 111 forms part of a system 501 and is mounted to robotic arm 503 for applying product directly to workpiece 505 during manufacturing and assembly thereof.
- the present invention has several advantages including the ability to produce single-walled carbon nanotubes in a continuous manner.
- the three-step process of the invention is scalable to large, industrial volume production levels.
- the plasma may be generated in several ways, including electrical resistance heating and/or electron beam vaporization of feedstock.
- the plasma is stabilized with radio frequency energy from inductance coils.
- a transition metal catalyst and associated catalyst support are used to form the swcnt end product.
- the present invention continuously produces large quantities of single wall carbon nanotubes.
- This method is superior to prior art processes because it provides for the continuous generation of carbon plasma, stabilization of the carbon plasma for homogenization of the reactant mixture and transport of a high concentration of carbon plasma to the product formation zone, and a continuous operation, flow-through reactor design.
- Controlling the feed rate of the feedstock, the pressure of the argon gas, and the electric power level, partial vaporization of the feedstock is controlled to a level such that the there is enough carbon remaining to allow a continuous line feed.
- the feedstock is vaporized with an electron beam, localized directional control of the energy and efficient energy transfer are achieved because of the highly conductive nature of the graphite.
- the second step of stabilization is much improved over the prior art.
- the stabilization step homogenizes the plasma energy density and concentration, leading to a more efficient reactor.
- the stabilization of the carbon plasma is achieved using radio frequency energy from inductance coils and, optionally, electrical resistance heaters inside the reactor to promote a higher concentration of carbon vapor in the reactor.
- the entire apparatus is designed so that it can be mounted vertically such that continuous deposition of product can be applied with precision using an overhead robotic arm.
- employing the apparatus of the present invention for manufacturing applications provides outstanding advantages over prior art devices and assembly techniques.
- the apparatus can be used to provide direct manufacturing of unitized structures using “mix and pour” processing, such that no tooling, fixtures, or part assembly are required.
- the elimination of these traditional assembly steps yields revolutionary performance.
- an apparatus constructed in accordance with the present invention theoretically yields a 68 to 78% weight reduction for some aircraft unitized wing boxes.
Abstract
Description
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US10/455,767 US7261779B2 (en) | 2003-06-05 | 2003-06-05 | System, method, and apparatus for continuous synthesis of single-walled carbon nanotubes |
PCT/US2004/017810 WO2004108591A2 (en) | 2003-06-05 | 2004-06-04 | System, method, and apparatus for continuous synthesis of single-walled carbon nanotubes |
EP04754421.8A EP1644287B1 (en) | 2003-06-05 | 2004-06-04 | Method, and apparatus for continuous synthesis of single-walled carbon nanotubes |
US11/834,210 US7763231B2 (en) | 2003-06-05 | 2007-08-06 | System and method of synthesizing carbon nanotubes |
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Cited By (31)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20100025225A1 (en) * | 2003-06-10 | 2010-02-04 | Plasmet Corporation | Continuous production of carbon nanomaterials using a high temperature inductively coupled plasma |
US20100150815A1 (en) * | 2008-12-17 | 2010-06-17 | Alfredo Aguilar Elguezabal | Method and apparatus for the continuous production of carbon nanotubes |
US20100227058A1 (en) * | 2005-12-09 | 2010-09-09 | Tsinghua University | Method for fabricating carbon nanotube array |
KR101054963B1 (en) * | 2008-09-23 | 2011-08-05 | 현대하이스코 주식회사 | Mold coating method and mobile coating device for same |
WO2012037042A1 (en) | 2010-09-14 | 2012-03-22 | Applied Nanostructured Solutions, Llc | Glass substrates having carbon nanotubes grown thereon and methods for production thereof |
US8158217B2 (en) | 2007-01-03 | 2012-04-17 | Applied Nanostructured Solutions, Llc | CNT-infused fiber and method therefor |
US8168291B2 (en) | 2009-11-23 | 2012-05-01 | Applied Nanostructured Solutions, Llc | Ceramic composite materials containing carbon nanotube-infused fiber materials and methods for production thereof |
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Also Published As
Publication number | Publication date |
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EP1644287A2 (en) | 2006-04-12 |
WO2004108591A2 (en) | 2004-12-16 |
WO2004108591A3 (en) | 2005-08-18 |
US20080170983A1 (en) | 2008-07-17 |
EP1644287B1 (en) | 2014-12-24 |
US7763231B2 (en) | 2010-07-27 |
US20040245088A1 (en) | 2004-12-09 |
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